Heterocyclic pigments and dyes

ABSTRACT

A compound of formula I ##STR1## in which each R 1  independently is selected from oxygen, ═NH or ═N--R 2  where R 2  is an aromatic or heteroaromatic group, provided not more than two groups R 1  are selected from oxygen and ═NH.

The invention relates primarily to pigments or solvent dyes, suitablefor pigmenting or dyeing plastics in the mass.

According to the invention, there is provided a compound of formula I##STR2## in which each R₁ independently is selected from oxygen, ═NH or═N--R₂ where R₂ is an aromatic or heteroaromatic group, provided notmore than two groups R₁ are selected from oxygen and ═NH.

Preferably when R₂ is an aromatic group, it is a group of formula α or β##STR3## where

n is 0, 1, 2 or 3 and

each R₅ independently is selected from halogen, (C₁₋₄alkyl)aminocarbonyl, (C₁₋₄ alkyl)carbonylamino, carboxyl, (C₁₋₄alkoxy)carbonyl, phenlaminocarbonyl, benzoylamino or phenyloxycarbonylor R₅ is a group of formula δ ##STR4## where each R₁₀ independently ishydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, cyan or nitro; provided notmore than one group R₅ attached to any one phenyl group is a group offormula δ.

Preferably each R₁₀ is hydrogen.

Preferably when R₂ is a heteroaromatic group, it is a thienyl,thiazolyl, pyrazolyl, imidazolyl, benzthiazolyl or benzimidazolyl group.

Preferably R₁ is R₁ ' where each R₁ ' independently is selected fromoxygen, ═NH and ═N--R₂ where R₂ is a group of formula α, provided thatnot more than two groups R₁ ' in the compound of formula I are selectedfrom oxygen and ═NH.

More preferably R₁ is R₁ " where each group R₁ " independently is ═N--R₂' where R₂ ' is a group of formula α' ##STR5## where

N' is 2 or 3; and

each R₅ ' independently is chloro, bromo, (C₁₋₄ alkyl)aminocarbonyl,(C₁₋₄ alkyl)carbonylamino, carboxyl, (C₁₋₄ alkoxy)carbonyl,phenylaminocarbonyl, benzoylamino, phenoxycarbonyl or a group of formulaδ' ##STR6##

provided that not more than one group R₅ ' attached to any one phenylgroup is a group of the formula δ'.

Most preferably R₁ is R₁ '" where each group R₁ '" independently is═N--R₂ " where R₂ " is a group of the formula α" ##STR7## where

n' is 2 or 3; and

each R₅ " independently is benzoylamino, chloro or bromo.

Especially preferred R₁ '" is R₁ ^(IV) where each R₁ ^(IV) independentlyis ═N--R₂ '" where R₂ '" is a group of formula α'", α^(IV) and α^(V)##STR8## where each R₁₀ independently is selected from Br and Cl.

Preferred groups of R₂ '" are of formula α^(VI) -α^(VIII) ##STR9##Compounds of formula I can be prepared by reacting one mole of thecompound of formula II ##STR10## with

(a) four moles of a compound of formula III

    R.sub.1 --NH.sub.2                                         (III)

or

(b) three moles of a compound of formula III and one mole of water orammonia; or

(c) two moles of a compound of formula III and two moles of water orammonia or one mole of water and one mole of ammonia.

The compounds of formula II and III are known or may be made from knowncompounds by known methods.

The reaction of the compound of formula II with a compound of formulaIII can take place at an elevated temperature, preferably from 80°-120°C. according to known methods.

The compounds of formula I are useful for dyeing in the mass plasticsmaterial. By the term "dyeing in the mass" is meant dyeing insolvent-containing masses, dyeing in solvent free masses and dyeing inplastics resins, by known methods.

Such processes include colouring oil based or water based paints orlacquers, spin dyeing from viscose or cellulose acetate, pigmenting ofpolyethylene, polystyrene, polyvinylchloride, rubber and artificalleather.

The compounds of formula I can also be used for print dyeing of graphicfabrics, for dyeing paper masses, for coating textiles or for pigmentsprinting.

Compounds of formula I where R₁ is ═N--R₂ where R₂ is a group of formulaα, n'=2 or 3 of and where R₅ is R₅ " are pigments. The remainingcompounds are suitable for mass dyeing of polyester melts in which theytend to form a homogeneous solution.

The dyeings, especially the pigment dyeings, have good heat fastness,good light fastness, good weather fastness, good fastness to chemicals,good migration fastness, good fastness to blooming, good fastness toovercoating, good fastness to solvents. The dyeing strength is good andthe compounds have good application properties, for instance goodflocculation ability, good crystallinity and good dispersability.

The invention will now be illustrated by the following Examples in whichall temperatures are in ° C.

EXAMPLE 1

18.15 g of the compound of formula II ##STR11## are dispersed in 100 mlsof ortho dichlorobenzene whilst stirring at 120° C. The dispersion iscooled to 100° C. and mixed with 49.0 g of 2,4,5 trichloroaniline in 150mls of ortho dichlorobenzene. The resulting mixture is heated to 110° C.and stirred at this temperature for 12 hours. The resulting pigment isof formula 1a ##STR12## The pigment of formula 1a is filtered hot andthen washed with ortho dichlorobenzene, methanol and finally water.

(a) The pigment can be used as such without any further treatment fordyeing or pigmenting of plastics and lacquers. By incorporating thepigment into a clear lacquer containing pigment and TiO₂ in a ratio of1:10, a reddish yellow colouring of the lacquer is produced with goodfastness properties. Such a dyeing has a colorimetric value ofH*(Hue)=60.27, C*(Chroma)=52.12, and L*(Lightness)=77.69.

(b) The pigment may, instead of being used directly, be recrystallisedin dimethylformamide and a β modification is formed having an X raypattern significantly different to the α-form. The β modification canalso be used to dye or pigment directly in plastics and lacquers. Whenthe pigment is added to a clear commercially availablealkyl-melamine-formaldehyde a yellowish colouring is imparted to thelacquer with good fastness properties. The Colorimetric Values in aclear lacquer containing pigment and TiO₂ in a 1:10 ratio is H*=70.82,C*=63.66 and L*=82.06.

The X-ray data for the α-modification is: 5.6(w); 4.18(w); 3.99(w);3.81(w); 3.57(w); 3.53(w); 3.45(w); 3.34(w); 3.22(w); 2.94(w).

The X-ray data for the β-modification is: 10.6(w); 6.5(w); 6.2(w);5.8(w); 4.4(w); 3.5(w); 3.35(w); 3.11(w).

in which w is weak.

EXAMPLES 2 to 10

Compounds of the formula I ##STR13## where R₁ is defined in the Tablebelow can be prepared from appropriate reactant according to the methodof Example 1.

    ______________________________________                                                         Nuance                                                                        of     Colorimetric                                          Ex.  R.sub.1           Dyeing   H*   C*   L*                                  ______________________________________                                        2    2,5-dichloro-4-benzoylamino-                                                                    orange   43.73                                                                              50.90                                                                              67.45                                    phenylimino                                                              3    2,5-dichlorophenylimino                                                                         yellow   76.60                                                                              50.59                                                                              86.19                               4    3,4-dibromophenylimino                                                                          brown-   74.34                                                                              42.97                                                                              70.10                                                      ish-                                                                          yellow                                                 5    2,5-dibromophenylimino                                                                          yellow   80.40                                                                              56.22                                                                              85.60                               6    2,5-dichloro-4-bromophenyl-                                                                     reddish- 59.31                                                                              52.39                                                                              76.60                                    imino             yellow                                                 7    2-bromo-4,5-dichlorophenyl-                                                                     reddish- 63.94                                                                              58.22                                                                              79.05                                    imino             yellow                                                 8    2,4-dibromophenylimino                                                                          yellow   70.83                                                                              58.11                                                                              81.46                               9    2,4-dichlorophenylimino                                                                         yellow   --   --   --                                  10   2,5-dichloro-4-acetylamino-                                                                     brown    --   --   --                                       phenylimino       yellow                                                 ______________________________________                                    

APPLICATION EXAMPLE

4 g of the β modification of Example 1 and 40 g of titanium dioxidepigment are milled in a ball mill for 24 hours with 96 g of a mixture of

50 g of a 60% solution of coco-aldehyde-melamine resin (with 32% fattycontent) in xylene;

30 g of a 50% melamine resin solution in butan-1-ol;

10 g of xylene; and

6 g of ethylene glycolmonoethyl ether.

The resulting dispersion is sprayed on an aluminium piece, air dried for30 minutes and stored for 30 minutes at 120° C. A brilliant yellow filmresults with good light and weathering fastnesses.

The Application Example can be repeated using, instead of 4 g of βmodification of Example, 4 g of any one of the products of Examples 2 to10 or of the α modification of Example 1.

What is claimed is:
 1. A compound of formula I ##STR14## in which eachR₁, independently, is oxygen, ═NH or ═N--R₂ where R₂ is a thienyl,pyrazolyl, imidazolyl, benzthiazolyl or benzimidazolyl group or a groupof formula α or β ##STR15## where n' is 2 or 3 and each R₅,independently, is halogen, (C₁₋₄ alkyl)aminocarbonyl, (C₁₋₄alkyl)carbonylamino, carboxyl, (C₁₋₄ alkoxy)carbonyl,phenylaminocarbonyl, benzoylamino, phenoxycarbonyl or a group of formulaδ ##STR16## where each R₁₀, independently, is hydrogen, halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, cyano or nitro, provided not more than one group R₅attached to any one phenyl group is a group of formula δ; provided thatnot more than two groups R₁ are selected from oxygen and ═NH.
 2. Acompound of formula I' ##STR17## in which each R'₁, independently, isoxygen, ═NH or ═N--R₂ where R₂ is a group of formula α ##STR18## wheren' is 2 or 3 and each R₅, independently, is halogen, (C₁₋₄alkyl)aminocarbonyl, (C₁₋₄ alkyl)carbonylamino, carboxyl, (C₁₋₄alkoxy)carbonyl, phenylaminocarbonyl, benzoylamino, phenoxycarbonyl or agroup of formula δ ##STR19## where each R₁₀, independently, is hydrogen,halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, cyano or nitro; provided not more thanone group R₅ attached to any one phenyl group is a group of formula δ;provided that not more than two groups R'₁ are selected from oxygen and--NH.
 3. A compound according to claim 2 in which R₁ ' is R₁ " whereeach group R₁ " independently is ═N--R₂ ' where R₂ ' is a group offormula α' ##STR20## where n' is 2 or 3 andeach R'₅ independently isselected from chloro, bromo, (C₁₋₄ alkyl)aminocarbonyl, (C₁₋₄alkyl)carbonylamino, carbonyl, (C₁₋₄ alkoxy)carbonyl,phenylaminocarbonyl, benzoylamino, phenoxycarbonyl or a group of formulaδ' ##STR21## provided that not more than one group R₅ ' attached to anyone phenyl group is a group of formula δ'.
 4. A compound according toclaim 2 in which R₁ ' is R₁ '" where each group R₁ '" independently is═N--R₂ " where R₂ " is a group of formula α" ##STR22## where n' is 2 or3; andeach R₅ " independently is benzoylamino, chloro or bromo.
 5. Acompound according to claim 2 in which R₁ ' is R₁ ^(IV) where each R₁^(IV) independently is ═N--R₂ '" where R₂ '" is a group of formula α'"to α^(V) ##STR23## where each R₁₀ independently is chloro or bromo.
 6. Acompound according to claim 1 of formula I in which R₁ is ═N--R₂ whereR₂ '" is a group of the formula α^(VI) to α^(VIII) ##STR24##
 7. Acompound according to claim 1 wherein each R₁₀ is hydrogen.
 8. Acompound according to claim 2 wherein each R₁₀ is hydrogen.
 9. Acompound according to claim 2 wherein each group R₁ ' is the same and isselected from the group consisting of 2,4,5-trichlorophenylimino,2,5-dichloro-4-benzoylaminophenylimino, 2,5-dichlorophenylimino,3,4-dibromophenylimino, 2,5-dibromophenylimino,2,5-dichloro-4-bromophenylimino, 2-bromo-4, 5-dichlorophenylimino,2,4-dibromophenylimino, 2,4-dichlorophenylimino and2,5-dichloro-4-acetylaminophenylimino.
 10. The compound according toclaim 7 of the formula ##STR25##
 11. The α-modification of the compoundof claim 8 having the following X-ray data: 5.6(w), 4.18(w), 3.99(w),3.8'(w), 3.57(w), 3.53(w), 3.45(w), 3.34(w), 3.22(w), 3.22(w), 2.94(w),in which w is weak.
 12. The β-modification of the compound of claim 8having the following X-ray data: 10.6(w), 6.5(w), 6.2(w), 5.8(w),4.4(w), 3.5(w), 3.35(w), 3.11(w), in which w is weak.